JP2015137211A - Hydrogen generation apparatus and method for operating the same, and fuel cell system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for reducing adverse effects caused by temperature fluctuation of hydrogen-containing gas which is recycled to a hydrogenation desulfurizer, as a method for operating a hydrogen generation apparatus.SOLUTION: The method for operating a hydrogen generation apparatus 100 comprises at least one of the steps of : condensing and separating moisture in hydrogen-containing gas by cooling at least any one of the hydrogen-containing gas before flowing in a recycle flow path 6, and the hydrogen-containing gas after flowing in the recycle flow path 6, the recycle flow path being a flow path for recycling a part of the hydrogen-containing gas and feeding the recycled hydrogen-containing gas to a hydrogenation desulfurizer; increasing a ratio of an oxygen-containing gas feed amount to a reformer 4 to a raw material gas feed amount to the reformer 4 when the temperature of the hydrogen-containing gas after going through the step of gas-liquid separation falls; and decreasing a ratio of the hydrogen-containing gas flowing in the recycle flow path 6 out of the hydrogen-containing gas.

Description

  The present invention relates to a hydrogen generator, an operation method thereof, and a fuel cell system including the hydrogen generator. More specifically, the present invention relates to a hydrogen generator equipped with a hydrodesulfurizer, a method for operating the hydrogen generator, and a fuel cell system including the hydrogen generator.

  Patent Document 1 discloses a desulfurizer that performs desulfurization treatment of a raw fuel containing hydrocarbons supplied through a raw fuel supply passage, and a reforming reaction of the raw fuel after desulfurization treatment in the presence of water vapor, thereby providing a hydrogen-containing gas. A reformer that generates hydrogen, a fuel cell unit that performs a power generation reaction using a hydrogen-containing gas that is supplied from the reformer through a hydrogen-containing gas supply path, a middle of the hydrogen-containing gas supply path, and a raw fuel supply path And a recycle gas supply path for connecting a part of the hydrogen-containing gas generated in the reformer to the raw fuel supply path, and a hydrogen-containing gas that passes through the recycle gas supply path. Disclosed is a solid oxide fuel cell system comprising a condenser for condensing moisture contained in a section and a discharger for discharging condensed water condensed by the condenser in the middle of a recycle gas supply path. 2). In such a configuration, there is a description that moisture can be effectively removed from the hydrogen-containing gas added to the raw fuel, and that moisture can be prevented from being mixed into the raw fuel supply path and moisture can be prevented from being mixed into the pressure increasing means (paragraph 0009). .

JP 2011-216308 A

  In the conventional solid oxide fuel cell system, the influence when the temperature of the hydrogen-containing gas added to the raw fuel fluctuates has not been sufficiently evaluated.

  The present invention addresses the above-described conventional problems, and aims to reduce adverse effects caused by temperature fluctuations of a hydrogen-containing gas recycled to a hydrodesulfurizer in a hydrogen generator and a fuel cell system including the hydrogen generator. And

  One aspect of the operation method of the hydrogen generator of the present invention is a step of removing sulfur compounds in a raw material by a hydrodesulfurizer, and a steam and the hydrodesulfurizer are supplied by a reformer. When a flow path for generating a hydrogen-containing gas using a raw material and a flow path for recycling a part of the hydrogen-containing gas and supplying it to the hydrodesulfurizer is used as a recycle flow path, the flow into the recycle flow path At least one of the previous hydrogen-containing gas and the hydrogen-containing gas after flowing into the recycle channel is cooled, and the condensed water generated from the hydrogen-containing gas is separated into gas and liquid, and the gas and liquid are separated. When the temperature of the hydrogen-containing gas that has undergone the step decreases, the ratio of the oxygen-containing gas supply amount to the reformer with respect to the raw material supply amount to the reformer is increased; and Comprising the at least one of steps to reduce the ratio of hydrogen-containing gas flowing into the recycle flow path of the gas.

  One aspect of the hydrogen generator of the present invention is an improved hydrodesulfurizer that removes sulfur compounds in a raw material, and a hydrogen-containing gas that is generated using steam and the raw material supplied from the hydrodesulfurizer. A recycle channel for recycling a part of the hydrogen-containing gas discharged from the reformer and supplying it to the hydrodesulfurizer, and a hydrogen-containing gas before flowing into the recycle channel And a gas-liquid separator that cools at least one of the hydrogen-containing gas after flowing into the recycle channel and condenses and separates moisture in the hydrogen-containing gas, and a hydrogen-containing gas supply amount to the reformer A gas supply amount ratio adjuster for adjusting a ratio of an oxygen-containing gas supply amount to the reformer, and a hydrogen to the reformer when the temperature of the hydrogen-containing gas after passing through the gas-liquid separator decreases. For gas supply As the ratio of the oxygen-containing gas supply amount to Kiaratame reformer is increased, and a controller for controlling the gas supply amount ratio regulator.

  One aspect (aspect) of the fuel cell system of the present invention includes the hydrogen generation device and a fuel cell that generates electric power using a hydrogen-containing gas supplied from the hydrogen generation device.

  According to one aspect of the present invention, in a hydrogen generator and a fuel cell system including the same, an adverse effect caused by temperature fluctuations of the hydrogen-containing gas recycled to the hydrodesulfurizer can be reduced.

FIG. 1 is a block diagram illustrating an example of a schematic configuration of a hydrogen generator according to the first embodiment. FIG. 2 is a block diagram illustrating an example of a schematic configuration of the hydrogen generator according to the first embodiment. FIG. 3 is a diagram showing an example of the relationship between the temperature of the recycle gas after passing through the gas-liquid separator and the amount of water supplied to the reformer. FIG. 4 is a block diagram illustrating an example of a schematic configuration of the hydrogen generator according to the second embodiment. FIG. 5 is a block diagram illustrating an example of a schematic configuration of the hydrogen generator according to the third embodiment. FIG. 6 is a block diagram showing an example of a schematic configuration of a fuel cell system according to the third embodiment.

  In the conventional hydrogen generator, when the cooling temperature after passing through the gas-liquid separator fluctuates, the amount of steam contained in the recycle gas after passing through the gas-liquid separator fluctuates, and the steam supply to the reformer The amount also fluctuated, but the effect was not studied.

  For example, when the recycle gas, which is a part of the hydrogen-containing gas produced by the reformer, is cooled with a refrigerant and the moisture in the recycle gas is condensed and separated and then supplied to the hydrodesulfurizer, it is condensed and separated. Water does not return to the reformer. Therefore, for example, when the temperature of the refrigerant decreases with a decrease in the outside air temperature, the temperature of the recycle gas after being cooled with the refrigerant decreases, the amount of water vapor in the recycle gas decreases, and the O / O of the gas in the reformer decreases. C becomes low. As a result, there is a problem that the possibility of carbon deposition on the reforming catalyst is increased.

  Here, O / C is an abbreviation for Oxygen / Carbon, and is the ratio of the number of oxygen atoms (mol) contained in the entire gas supplied to the reformer to the number of carbon atoms (mol). O / C is generally used as one of the indicators of the possibility of carbon deposition.

  As a method for dealing with the above problems, it is conceivable that the water supply amount during normal operation is excessively increased in advance so that the amount of water vapor in the recycle gas is not affected by the change in the outside air temperature. However, since excessive water is converted into steam and supplied to the reformer, there is a problem that energy efficiency is lowered.

  Therefore, the present inventors have come up with the idea of adjusting the gas supply ratio so that the fluctuation of O / C is reduced according to the temperature of the recycle gas after passing through the gas-liquid separator. Specifically, for example, when the temperature of the recycle gas after being cooled is decreased, the ratio of the supply amount of the oxygen-containing gas to the reformer with respect to the supply amount of the hydrogen-containing gas to the reformer is increased. That is, O / C fluctuations can be reduced by adjusting the ratio of the hydrogen-containing gas supply amount and the oxygen-containing gas supply amount based on the raw material supply amount to the reformer.

  More specifically, for example, reducing the supply amount of recycle gas (hydrogen-containing gas) to the reformer, reforming steam (a type of oxygen-containing gas), based on the raw material supply amount to the reformer It is conceivable to increase the supply amount to the reformer, to increase the supply amount of air (a kind of oxygen-containing gas) to the reformer.

  In such a configuration, the temperature of the gas recycled to the hydrodesulfurizer should decrease and the O / C should decrease if it was originally, but the O / C would decrease by adjusting the gas supply ratio. Since it becomes difficult, the possibility that carbon on the reforming catalyst is deposited can be reduced.

  Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.

  Each of the embodiments described below shows a specific example of the present invention. Numerical values, shapes, materials, components, arrangement positions and connection forms of components, steps, order of steps, and the like shown in the following embodiments are merely examples, and do not limit the present invention. In addition, among the constituent elements in the following embodiments, constituent elements that are not described in the independent claims indicating the highest concept of the present invention are described as optional constituent elements. In the drawings, the same reference numerals are sometimes omitted. Further, the drawings schematically show each component for easy understanding. Moreover, in a manufacturing method, the order of each process etc. can be changed as needed, and another well-known process can be added.

(First embodiment)
The operation method of the hydrogen generator according to the first embodiment includes a step of removing sulfur compounds in a raw material with a hydrodesulfurizer, and a hydrogen gas using a steam and a raw material supplied from the hydrodesulfurizer with a reformer. The step of generating the containing gas and the hydrogen containing gas before flowing into the recycling passage when the passage for recycling a part of the hydrogen containing gas and supplying it to the hydrodesulfurizer is used as the recycling passage. At least one of the hydrogen-containing gas after flowing into the flow path is cooled, and the temperature of the hydrogen-containing gas that has undergone the gas-liquid separation of the condensed water generated from the hydrogen-containing gas and the step of gas-liquid separation is determined. If it decreases, the step of increasing the ratio of the oxygen-containing gas supply amount to the reformer with respect to the raw material supply amount to the reformer and the ratio of the hydrogen-containing gas flowing into the recycle flow path among the hydrogen-containing gas And a at least one of steps be reduced.

  With such a configuration, it is possible to reduce adverse effects caused by temperature fluctuations of the hydrogen-containing gas recycled to the hydrodesulfurizer.

  In the above operation method, the step of increasing the ratio of the oxygen-containing gas supply amount to the raw material supply amount to the reformer is a step of increasing the ratio of the steam supply amount to the reformer with respect to the raw material supply amount to the reformer. It may be.

  In the above operation method, the step of increasing the ratio of the oxygen-containing gas supply amount to the raw material supply amount to the reformer increases the reforming air supply amount to the reformer with respect to the raw material supply amount to the reformer. It may be a step.

  In the above operation method, the step of increasing the ratio of the oxygen-containing gas supply amount to the raw material supply amount to the reformer is the step of increasing the hydrogen-containing gas to the reformer via the recycle channel with respect to the raw material supply amount to the reformer. It may be a step of reducing the supply amount.

  The hydrogen generator of the first embodiment includes a hydrodesulfurizer that removes sulfur compounds in a raw material, a reformer that generates hydrogen-containing gas using steam and a raw material supplied from the hydrodesulfurizer, and a reformer. Recycle channel for recycling a part of the hydrogen-containing gas discharged from the gasifier and supplying it to the hydrodesulfurizer, hydrogen-containing gas before flowing into the recycle channel, and after flowing into the recycle channel A gas-liquid separator that cools at least one of the hydrogen-containing gas and condenses and separates moisture in the hydrogen-containing gas; and a ratio of an oxygen-containing gas supply amount to the reformer with respect to a raw material supply amount to the reformer; When the temperature of the hydrogen-containing gas after passing through the gas-liquid separator and the gas supply amount ratio regulator that adjusts at least one of the ratio of the hydrogen-containing gas flowing into the recycling flow path among the hydrogen-containing gas, Raw material to reformer Executing at least one of increasing the ratio of the oxygen-containing gas supply amount to the reformer with respect to the supply amount and decreasing the ratio of the hydrogen-containing gas flowing into the recycle flow path among the hydrogen-containing gas, And a controller for controlling the gas supply amount ratio adjuster.

  With such a configuration, it is possible to reduce adverse effects caused by temperature fluctuations of the hydrogen-containing gas recycled to the hydrodesulfurizer.

  In the hydrogen generation apparatus, the gas supply amount ratio adjuster includes a water vapor supply device that supplies water vapor to the reformer, and the controller increases the water vapor supply amount to the reformer, thereby supplying the reformer to the reformer. The ratio of the oxygen-containing gas supply amount to the reformer relative to the raw material supply amount may be increased.

  In the hydrogen generation apparatus, the gas supply amount ratio adjuster includes an air supply device that supplies air to the reformer, and the controller increases the air supply amount to the reformer, thereby supplying the reformer to the reformer. The ratio of the oxygen-containing gas supply amount to the reformer relative to the raw material supply amount may be increased.

  In the hydrogen generation apparatus, the gas supply amount ratio adjuster includes a flow rate adjuster that adjusts the supply amount of the hydrogen-containing gas to the reformer via the recycle flow path, and the controller is modified via the recycle flow path. The ratio of the oxygen-containing gas supply amount to the reformer with respect to the raw material supply amount to the reformer may be increased by reducing the hydrogen-containing gas supply amount to the quality device.

  FIG. 1 is a block diagram illustrating an example of a schematic configuration of a hydrogen generator according to the first embodiment. Hereinafter, the hydrogen generator 100 of the first embodiment will be described with reference to FIG.

  In the example shown in FIG. 1, the hydrogen generator 100 includes a hydrodesulfurizer 2, a reformer 4, a recycle channel 6, a gas-liquid separator 8, a gas supply amount ratio adjuster 10, and a controller. 12.

  The hydrodesulfurizer 2 removes sulfur compounds in the raw material. More specifically, the hydrodesulfurizer 2 adds and removes hydrogen from the sulfur compound in the raw material. As the hydrogen, for example, hydrogen contained in a hydrogen-containing gas discharged from the reformer 4 can be used. Specifically, for example, the hydrogen-containing gas discharged from the reformer 4 is supplied to the raw material supply path via the recycle channel 6 branched from the hydrogen-containing gas channel connected to the reformer 4. It may be supplied. The raw material supply path is a flow path for supplying the raw material to the hydrodesulfurizer 2.

  The raw material can be, for example, city gas containing methane as a main component, natural gas, gas containing an organic compound containing carbon and hydrogen as constituent elements, such as LPG, kerosene, and alcohol such as methanol and ethanol. City gas is gas supplied from gas companies to households through gas infrastructure.

  The sulfur compound may be artificially added to the raw material as an odorant component, or may be a natural sulfur compound derived from the raw material itself. Specifically, tertiary-butylmercaptan (TBM), dimethyl sulfide (DMS), tetrahydrothiophene (THT), carbonyl sulfide (COS), hydrogen sulfide, etc. Is exemplified.

  The hydrodesulfurizer 2 is filled with a hydrodesulfurizing agent. Examples of the hydrodesulfurization agent include a CuZn-based catalyst (for example, a Cu-Zn-Ni-based catalyst and a Cu--) having both a function of converting a sulfur compound into hydrogen sulfide by a hydrogenation reaction and a function of adsorbing hydrogen sulfide. Zn-Fe catalyst etc. can be used. The hydrodesulfurization agent is not limited to this example, and is a CoMo-based catalyst that converts a sulfur compound in the raw material gas into hydrogen sulfide, and a sulfur adsorbent that is provided downstream thereof to adsorb and remove hydrogen sulfide. You may comprise with at least any one of a ZnO type catalyst and a CuZn type catalyst.

  The hydrodesulfurization agent may be used after being heated to a predetermined temperature higher than normal temperature. The predetermined temperature is defined as a temperature necessary for hydrodesulfurization, and may be, for example, 200 to 300 degrees Celsius. In addition, as a heating method of the hydrodesulfurizer 2, the inflow gas temperature may be adjusted by heating the gas flowing into the hydrodesulfurizer 2.

  The hydrodesulfurizer 2 may be heated to adjust the reaction temperature inside the hydrodesulfurizer 2.

  The reformer 4 generates a hydrogen-containing gas using the raw material supplied from the steam and the hydrodesulfurizer. Examples of the reforming reaction that proceeds in the reformer 4 include a steam reforming reaction (SR) and an oxidative steam reforming reaction (OSR). Although not shown in FIG. 1, equipment required for each reforming reaction is provided as appropriate. For example, if the reforming reaction is a steam reforming reaction, a combustor that heats the reformer, an evaporator that generates steam, and a water supplier that supplies water to the evaporator may be provided.

  A reforming catalyst is disposed inside the reformer 4. With this reforming catalyst, the reforming reaction proceeds and a hydrogen-containing gas can be generated from the raw material and water. The heat required for the reforming reaction may be supplied from, for example, a combustor (not shown). In general, as the reforming catalyst, at least one selected from the group consisting of noble metal catalysts such as Pt, Ru and Rh and Ni is preferably used. In the hydrogen generator of the present embodiment, a reforming catalyst containing Ru is used. An alumina carrier impregnated with at least one of platinum and ruthenium may be used. The reformer 4 may be configured to incorporate an evaporator of a steam supply unit.

  The recycle flow path 6 is a flow path for recycling a part of the hydrogen-containing gas discharged from the reformer 4 and supplying it to the hydrodesulfurizer 2. The diversion ratio between the hydrogen-containing gas channel through which the hydrogen generator 100 supplies the hydrogen-containing gas to the outside and the recycle channel 6 may be adjusted by, for example, the pipe diameters of both channels, or at least You may adjust by installing a flow regulating valve in one of these flow paths.

  In the gas-liquid separator 8, at least one of the hydrogen-containing gas before flowing into the recycle channel 6 and the hydrogen-containing gas after flowing into the recycle channel 6 is cooled, and condensed water generated from the hydrogen-containing gas Hydrogen containing gas is separated. The configuration for cooling the hydrogen-containing gas may be a configuration in which the recycle channel 6 is naturally cooled. Moreover, the structure using the cooler which cools the hydrogen containing gas in the recycle flow path 6 with a refrigerant | coolant may be sufficient. As the refrigerant, for example, air in the housing, air taken from the outside, water in the hot water storage tank, or the like can be used. Liquid water generated by the gas-liquid separator 8 may be discharged to the outside of the hydrogen generator 100. In the figure, the gas-liquid separator 8 is provided in the recycle flow path 6, but the gas-liquid separator 8 is provided in the hydrogen-containing gas flow path upstream of the branch portion where the recycle flow path 6 branches. May be.

  The hydrogen-containing gas discharged from the gas-liquid separator 8 merges with the raw material and is supplied to the hydrodesulfurizer 2 at the junction of the recycle flow path 6 and the raw material supply path.

  The gas supply rate ratio adjuster 10 is a ratio of the oxygen-containing gas supply amount to the reformer 4 relative to the raw material supply amount to the reformer 4 and the ratio of the hydrogen-containing gas flowing into the recycle channel 6 among the hydrogen-containing gas. Adjust at least one of The hydrogen-containing gas supply amount to the reformer 4 is the amount of hydrogen-containing gas supplied to the hydrodesulfurizer 2. The hydrogen-containing gas is supplied to the reformer 4 via the hydrodesulfurizer 2.

  The hydrogen-containing gas here is a recycle gas (hydrogen-containing gas supplied to the reformer 4 via the recycle flow path 6, hereinafter referred to as “recycle gas”). The recycle gas contains carbon monoxide, carbon dioxide, unreformed raw materials, and the like derived from the reforming reaction in the reformer 4, and contains carbon atoms.

  The “ratio of the hydrogen-containing gas flowing into the recycle flow path 6 out of the hydrogen-containing gas” refers to a so-called diversion ratio. For example, the recycle flow path 6 with respect to the total amount of the hydrogen-containing gas generated by the reformer 4 It can be set as the ratio of the hydrogen-containing gas which flows in.

  The oxygen-containing gas is at least one of water vapor and air supplied to the reformer. The oxygen-containing gas contains oxygen atoms but does not substantially contain carbon atoms.

  O / C differs greatly between hydrogen-containing gas and oxygen-containing gas. It is supplied to the reformer 4 by adjusting the ratio of the oxygen-containing gas supply amount to the raw material supply amount, or by adjusting the ratio of the hydrogen-containing gas flowing into the recycle channel 6 among the hydrogen-containing gas. The O / C of the gas can be controlled. When the oxygen-containing gas is pure water vapor, the O / C of the oxygen-containing gas cannot be calculated (infinite), but increasing or decreasing the water vapor increases or decreases the oxygen supplied to the reformer. The O / C in the reformer can be controlled by adjusting the ratio of the steam supply amount.

  Specifically, as the gas supply amount ratio adjuster 10, for example, a water vapor supply device capable of adjusting a water vapor supply amount, a reforming air supply device capable of adjusting a reforming air supply amount, and a recycle gas supply amount The flow rate regulator etc. which can adjust are mentioned.

  When the temperature of the hydrogen-containing gas after passing through the gas-liquid separator 8 decreases, the controller 12 increases the ratio of the oxygen-containing gas supply amount to the reformer 4 with respect to the raw material supply amount to the reformer 4. Then, the gas supply amount ratio adjuster 10 is controlled so as to execute at least one of reducing the ratio of the hydrogen-containing gas flowing into the recycle channel 6 among the hydrogen-containing gas.

  The controller 12 only needs to have a control function, and includes an arithmetic processing unit (not shown) and a storage unit (not shown) that stores a control program. Examples of the arithmetic processing unit include an MPU and a CPU. An example of the storage unit is a memory. The controller may be composed of a single controller that performs centralized control, or may be composed of a plurality of controllers that perform distributed control in cooperation with each other.

When the temperature of the hydrogen-containing gas that has passed through the gas-liquid separator 8 decreases, the dew point of the hydrogen-containing gas decreases, and the amount of water contained in the hydrogen-containing gas decreases. As a result, the concentration of CO, CO ₂ and unreformed raw material increases with respect to water vapor, and the O / C of the hydrogen-containing gas decreases. If the decrease in O / C is left as it is, the O / C of the entire gas supplied to the reformer 4 decreases, and the possibility of carbon deposition increases. The decrease in O / C is thought to be because the amount of C atoms increases with respect to the amount of O atoms and carbon tends to become excessive.

  The temperature of the hydrogen-containing gas after passing through the gas-liquid separator 8 is detected by a detector (not shown) that detects this. This detector may be a detector that directly detects the temperature of the hydrogen-containing gas after passing through the gas-liquid separator 8 or may be a detector that detects indirectly. When the detector that indirectly detects the temperature of the hydrogen-containing gas after passing through the gas-liquid separator 8 adopts a configuration in which the recycle channel 6 is naturally cooled to cool the hydrogen-containing gas, The detector which detects the air temperature outside a housing | casing may be sufficient. Moreover, when the cooler which cools the hydrogen containing gas in the recycle flow path 6 with a refrigerant is used for cooling the hydrogen containing gas, the temperature of the hydrogen containing gas after passing through the gas-liquid separator 8 is indirectly set. The detector for detecting may be a detector for detecting the temperature of the refrigerant. Moreover, the detector which measures the time correlated with the said air temperature or refrigerant | coolant temperature may be sufficient. For example, since the temperature of air or water fluctuates in relation to the date and time, a detector that measures this temperature is used as a detector that indirectly detects the temperature of the hydrogen-containing gas after passing through the gas-liquid separator 8. It may be used. In addition, the specific structure of the detector which detects temperature or time is not specifically limited.

  According to the configuration of the present embodiment, when the temperature of the hydrogen-containing gas after cooling is decreased, the ratio of the oxygen-containing gas supply amount to the raw material supply amount is increased, or among the hydrogen-containing gas, the recycle flow path By reducing the ratio of the hydrogen-containing gas flowing into the reactor, it is possible to mitigate the decrease in O / C in the reformer 4 and reduce the possibility of carbon deposition.

(First embodiment)
FIG. 2 is a block diagram illustrating an example of a schematic configuration of the hydrogen generator according to the first embodiment. Hereinafter, the hydrogen generator 110 of the first embodiment will be described with reference to FIG.

  In the example shown in FIG. 2, the hydrogen generator 110 includes a hydrodesulfurizer 22, a reformer 24, a recycle gas channel 26, a gas-liquid separator 28, a temperature detector 30, and a raw material supply channel 34. A water vapor supply device 36, a controller 38, a water vapor supply channel 40, and a hydrogen-containing gas flow channel 42.

  The hydrodesulfurizer 22 and the reformer 24 can be configured similarly to the hydrodesulfurizer 2 and the reformer 4 provided in the hydrogen generator 100 of the first embodiment, respectively. The detailed explanation is omitted.

  The recycle gas flow path 26 branches off from the hydrogen-containing gas flow path 42, a gas / liquid separator 28 is provided instead of the gas / liquid separator 8, a temperature detector 30 is provided downstream thereof, and further condensed from the downstream side. Except for the point where the water flow path 32 is branched, the same structure as the recycle flow path 6 can be adopted.

  The gas-liquid separator 28 may have the same configuration as the gas-liquid separator 8 except that the generated liquid water is discharged through the condensed water flow path 32 branched from the recycle gas flow path 26. it can.

  The temperature detector 30 detects the temperature of the hydrogen-containing gas after passing through the gas-liquid separator 28. The specific configuration of the temperature detector 30 is not particularly limited. For example, the temperature detector 30 may directly detect the temperature of the hydrogen-containing gas after passing through the gas-liquid separator 28, or by detecting the temperature of the refrigerant that the gas-liquid separator 28 uses for cooling, The temperature of the hydrogen-containing gas after passing through the gas-liquid separator 28 may be detected indirectly.

  The condensed water channel 32 is a channel that branches from the recycle gas channel 26 and discharges the liquid water generated by the gas-liquid separator 28 to the outside of the hydrogen generator 110.

  The raw material supply path 34 is a flow path for supplying the raw material to the reformer 24. The raw material supply channel 34 is connected to the downstream end of the recycle gas channel 26 on the upstream side of the hydrodesulfurizer 22. With this configuration, the recycle gas is mixed with the raw material and supplied to the hydrodesulfurizer 22.

  Although not shown, a raw material flow rate adjuster may be provided in the raw material supply path 34. As the raw material flow rate adjuster, a fluid transfer device such as a diaphragm pump may be used, or a flow rate adjusting valve such as a needle valve may be used.

  The steam supply unit 36 generates steam from liquid water and supplies the steam to the reformer 24 through the steam supply path 40. The liquid water supplied to the water vapor supply device 36 may be supplied from the outside of the hydrogen generator 110, or may be liquid water discharged from the gas-liquid separator 28 through the condensed water channel 32, for example. .

  The water vapor supply device 36 includes an evaporator that generates water vapor and a water supply device that supplies water to the evaporator. As the water supply device, for example, a displacement pump such as a gear pump and a plunger pump may be used. The evaporator may be configured to be heated by, for example, an electric heater, a combustion gas from a combustor, or the like.

  The steam supply unit 36 is configured to be able to adjust the amount of steam supplied to the reformer 24. Specifically, the amount of heat supplied to the evaporator and / or liquid water may be controlled, or the amount of water vapor generated in the evaporator may be sent to the reformer 24 by a flow rate adjustment valve or the like. You may control.

  When the temperature of the hydrogen-containing gas after passing through the gas-liquid separator 8 decreases, the controller 38 increases the ratio of the oxygen-containing gas supply amount to the reformer 4 with respect to the raw material supply amount to the reformer 4. Thus, the water vapor supply device 36 is controlled. That is, in the first example, the water vapor supplier 36 corresponds to the gas supply amount ratio adjuster 10 of the first embodiment. The oxygen-containing gas in the first embodiment includes water vapor.

  When the temperature of the hydrogen-containing gas after passing through the gas-liquid separator 8 decreases, the controller 38 increases the steam supply amount to the reformer 24 relative to the raw material supply amount to the reformer 24. The feeder 36 is controlled. At this time, the raw material supply amount to the reformer 24 may be constant.

  For example, when the required amount of hydrogen increases in the hydrogen utilization device that supplies the hydrogen-containing gas from the hydrogen generator 110 and the amount of raw material supplied to the reformer 24 increases, the raw material is supplied to the reformer 24. The amount of steam supplied to the reformer 24 may be increased more than the amount increases.

  For example, when the hydrogen generation apparatus 110 supplies hydrogen-containing gas and the required amount of hydrogen decreases in the hydrogen utilization device, the raw material supply amount to the reformer 24 decreases. The amount by which the amount of steam supplied to the reformer 24 is increased may be reduced by the amount that is reduced.

  That is, “the amount of steam supplied to the reformer 24 relative to the amount of raw material supplied to the reformer 24” increases the amount of steam supplied relative to the amount of raw material supplied to the reformer 24. That means. Therefore, when the raw material supply amount to the reformer 24 decreases, if the steam supply amount increases relative to the raw material supply amount to the reformer 24, the steam supply amount does not need to be increased. It may be good or decreased.

  Except for the above points, the controller 38 can have the same configuration as the controller 12 of the first embodiment.

  FIG. 3 is a diagram showing an example of the relationship between the temperature of the recycle gas after passing through the gas-liquid separator 28 and the reforming water flow rate. The reforming water flow rate is the amount of water supplied to the evaporator, and is proportional to the supply amount of water vapor supplied from the water vapor supplier 36 to the reformer 24.

  As shown in the figure, as the temperature of the recycle gas after passing through the gas-liquid separator 28 becomes lower, the reforming water flow rate increases in order to suppress the decrease in O / C in the reformer 24. In other words, even if the temperature of the recycle gas after passing through the gas-liquid separator 28 is lowered, the steam supplied to the reformer 24 from the steam supplier 36 is increased by increasing the reforming water flow rate. By increasing the amount, the decrease in O / C inside the reformer 24 can be suppressed.

  Also in the present embodiment, the same modifications as in the first embodiment are possible.

(Example of simulation in the first embodiment)
[Example]
In the configuration of FIG. 2, the simulation result when the operation is performed based on the first embodiment, that is, the temperature and flow rate of each fluid obtained from the calculation of each part of the system and the entire substance and energy balance will be described.

  In the present embodiment, the reforming water supply flow rate is controlled by an instruction from the controller 38 based on the temperature of the recycle gas after passing through the gas-liquid separator 8 detected by the temperature detector 30.

  The reforming water flow rate is controlled by the steam supply unit 36 using a correlation equation between the temperature of the recycle gas after passing through the gas-liquid separator 8 and the reforming water flow rate as shown in FIG.

  The control may be performed using a correlation formula between the temperature of the recycle gas after passing through the gas-liquid separator 8 and the set value of O / C. In this embodiment, the preset O / C in the reformer 24 is 2.50.

  When the temperature of the recycle gas after passing through the gas-liquid separator 8 changes from 40 degrees Celsius to 5 degrees Celsius, the O / C in the reformer 24 is maintained at the preset O / C of 2.50. Therefore, the reforming water supply amount to the evaporator is changed by the instruction from the controller 38 so that the steam supply amount to the reformer 24 becomes 6.36 SLM.

  In this case, the set value of O / C calculated from the flow rate of reforming water supplied to the water vapor supply path 40 and the composition and flow rate of the raw material supplied to the raw material supply path 34 is 2.69.

  Here, when the temperature of the recycle gas after passing through the gas-liquid separator 8 is 5 degrees Celsius, the water vapor 0.45 SLM in the hydrogen-containing gas is condensed and separated by cooling and discharged to the condensed water flow path 15. .

  The hydrogen-containing gas 0.64 SLM from which the condensed water has been separated is supplied to the raw material supply path 34, joined with the fuel, and supplied to the hydrodesulfurizer 22.

Here, the recycle gas composition is composed of CH ₄ : H ₂ : H ₂ O: CO: CO _{2 in} a ratio (molar ratio) of 24.1: 58.4: 0.9: 2.3: 14.3. Is done.

  The 2.03 SLM city gas supplied from the raw material supply path 34 is combined with the recycle gas 0.64 SLM supplied from the recycle gas path 26 and supplied to the hydrodesulfurizer 22.

  Here, since the O / C of the recycle gas that merges from the recycle gas flow path 26 to the raw material supply path 34 is 0.78, the O / C of the merged gas in the reformer 2 is 2.50.

  As described above, the reformed water supply flow rate is controlled based on the temperature of the recycle gas after passing through the gas-liquid separator 8 detected by the temperature detector 30, thereby passing through the gas-liquid separator 8. Even when the temperature of the recycled gas after the change is changed to 5 degrees Celsius, the O / C in the reformer 2 can be kept constant at the preset 2.50. Therefore, even when the outside air temperature or the cooling water temperature is lowered, the possibility that carbon is precipitated in the reformer 24 can be reduced.

  In this embodiment, the reforming water flow rate is controlled by using a correlation equation or a correlation table prepared in advance between the temperature of the recycle gas after passing through the gas-liquid separator 8 and the reforming water flow rate. However, for example, a control method may be used in which a plurality of correlation equations or correlation tables are created, and the correlation equations or correlation tables used for control are changed monthly.

[Comparative example]
In the configuration of FIG. 2, the simulation results when the operation is performed based on the comparative example, that is, the temperature and flow rate of each fluid obtained from the calculation of each part of the system and the entire material and energy balance will be described.

  The 2.03 SLM city gas supplied from the raw material supply path 34 is combined with the recycle gas 0.63 SLM supplied from the recycle gas path 26 and supplied to the hydrodesulfurizer 22.

Here, the city gas composition is composed of CH ₄ : C ₂ H ₆ : C ₃ H ₈ : C ₄ H _{10 in} a ratio (molar ratio) of 88.9: 6.8: 3.1: 1.2. The The recycle gas composition is composed of CH ₄ : H ₂ : H ₂ O: CO: CO _{2 in} a ratio (molar ratio) of 25.5: 57.2: 0.9: 2.4: 14.0.

In this comparative example, the H ₂ concentration in the combined gas in the hydrodesulfurizer 22 is 13.5%, and the hydrodesulfurization reaction can sufficiently proceed. Note that the H ₂ concentration in the combined gas may be a concentration at which sulfur can be removed from the raw material gas by the hydrodesulfurizer 22.

  On the other hand, the reformed water supplied from the steam supply path 40 is evaporated by the steam supply unit 36 and 5.9 SLM of steam is supplied to the reformer 24.

  In this case, the O / C set value calculated from the flow rate of reforming water supplied to the water vapor supply path 40 and the composition and flow rate of the raw material supplied to the raw material supply path 34 is 2.50.

  Here, the O / C of the recycle gas after passing through the gas-liquid separator 8 until it joins the raw material supply path 34 has a temperature of the recycle gas after passing through the gas-liquid separator 8 of 5 degrees Celsius. In this case, since it is 0.75, the O / C of the combined gas in the reformer 24 is 2.32.

  In the reformer 24, the hydrocarbons in the combined gas are reformed into a hydrogen-containing gas by the steam reforming reaction under the condition of O / C = 2.32.

  In this comparative example, the reforming temperature is 500 degrees Celsius, but the reforming temperature is not limited to this, and may be any temperature in the range of 400 to 700 degrees Celsius, for example. .

The hydrogen-containing gas generated in the reformer 24 is CH ₄ : H ₂ : H ₂ O: CO: CO _{2 at} a ratio (moles) of 15.4: 34.5: 40.3: 1.4: 8.4. Ratio) and the O / C is 2.32.

  The hydrogen-containing gas 10.4 SLM generated by the reformer 24 is diverted into the hydrogen-containing gas flow path 42 and the recycle gas flow path 26 at a ratio of 90:10. The diversion ratio need not be a value limited to this, and may be any diversion ratio that enables sulfur removal by the hydrodesulfurizer 1.

  The hydrogen-containing gas 1.04 SLM supplied to the recycle gas flow path 26 is cooled to 5 degrees Celsius in the gas-liquid separator 28 by heat radiation to the atmosphere. By cooling, the water vapor 0.41 SLM in the hydrogen-containing gas is condensed and separated and discharged to the condensed water channel 32. The hydrogen-containing gas 0.63 SLM from which the condensed water has been separated is supplied to the raw material supply path 34, merged with the fuel as described above, and supplied to the hydrodesulfurizer 22, and as described above, the reformer 24. A hydrogen-containing gas is produced.

  As described above, when the temperature of the recycle gas after passing through the gas-liquid separator 8 is 5 degrees Celsius, the O / C in the reformer 24 is 2 versus the set O / C of 2.50. .32. Therefore, the subject that the risk of carbon deposition in the reformer 24 increases arises.

  In anticipation of a decrease in the outside air temperature, the O / C set value can be excessively increased in advance. In this case, however, in the case of a reforming reaction using steam, the amount of heat required for steam generation increases and efficiency increases. Decreases. In the case of the partial oxidation method, there is a problem that the efficiency is lowered by a part of the raw material being oxidized in the reformer.

  In addition, when supplying the hydrogen-containing gas to the fuel cell, the following problems occur due to the increase in O / C in the reformer 24. That is, when the oxygen-containing gas is water vapor, the Nernst voltage decreases, the stack voltage decreases, and the power generation efficiency decreases. When the oxygen-containing gas is air, a part of the fuel is oxidized by oxygen in the air in the reformer and cannot be used in the stack, resulting in a reduction in power generation efficiency.

(Second embodiment)
FIG. 4 is a block diagram illustrating an example of a schematic configuration of the hydrogen generator according to the second embodiment. Hereinafter, the hydrogen generator 120 of the second embodiment will be described with reference to FIG.

  In the example shown in FIG. 4, the hydrogen generator 120 includes a flow rate regulator 44.

  The flow rate regulator 44 adjusts the hydrogen-containing gas supply amount to the reformer 24 via the recycle gas flow path 26. The flow rate regulator 44 can be configured by, for example, a pump and a needle valve. In FIG. 4, the flow rate regulator 44 is provided on the downstream side of the gas-liquid separator 28, but the flow rate regulator 44 may be provided on the upstream side of the gas-liquid separator 28.

  When the temperature of the hydrogen-containing gas after passing through the gas-liquid separator 8 decreases, the controller 38 adjusts the flow rate regulator so that the ratio of the hydrogen-containing gas flowing into the recycle gas passage 26 out of the hydrogen-containing gas decreases. 44 is controlled. That is, in the second example, the flow rate regulator 44 corresponds to the gas supply amount ratio regulator 10 of the first embodiment.

  When the temperature of the hydrogen-containing gas after passing through the gas-liquid separator 8 decreases, the controller 38 adjusts the flow rate regulator so that the ratio of the hydrogen-containing gas flowing into the recycle gas passage 26 out of the hydrogen-containing gas decreases. 44 is controlled. The ratio of the hydrogen-containing gas flowing into the recycle gas passage 26 among the hydrogen-containing gas is related to the supply amount of the hydrogen-containing gas to the hydrodesulfurizer 22. At this time, the raw material supply amount to the reformer 24 may be constant.

  For example, when the required amount of hydrogen increases in the hydrogen utilization device that supplies the hydrogen-containing gas from the hydrogen generator 110 and the amount of raw material supplied to the reformer 24 increases, the raw material is supplied to the reformer 24. The extent to which the amount of hydrogen-containing gas supplied to the reformer 24 is decreased may be reduced by the increase in the amount.

  For example, when the hydrogen generation apparatus 110 supplies hydrogen-containing gas and the required amount of hydrogen decreases in the hydrogen utilization device, the raw material supply amount to the reformer 24 decreases. The amount of hydrogen-containing gas supplied to the reformer 24 may be increased by the amount that decreases.

  That is, “the ratio of the hydrogen-containing gas flowing into the recycle gas passage 26 in the hydrogen-containing gas decreases” means that the amount of hydrogen-containing gas generated by the reformer 24 flows into the recycle gas passage 26. It means to relatively reduce the ratio of the amount of hydrogen-containing gas to be produced.

  Except for the above points, the controller 38 can have the same configuration as the controller 12 of the first embodiment.

  In addition, except for the above points, the hydrogen generator 120 can have the same configuration as the hydrogen generator 110 of the first embodiment. Therefore, the same reference numerals and names are used for the same components in FIG. 4 and FIG. 2, and detailed description thereof is omitted.

  Even if the temperature of the recycle gas after passing through the gas-liquid separator 8 is lowered, the supply amount of the hydrogen-containing gas to the reformer 24 is reduced, that is, the recycle gas is supplied from the steam supply device 36 to the reformer 24. By reducing the hydrogen-containing gas, the decrease in O / C inside the reformer 24 can be suppressed.

  Also in the present embodiment, the same modifications as in the first embodiment are possible. The first embodiment and the second embodiment may be combined.

(Example of simulation in the second embodiment)
In the configuration of FIG. 4, the simulation result when the operation is performed based on the second embodiment, that is, the temperature and flow rate of each fluid obtained from the calculation of each part of the system and the entire material and energy balance will be described. The temperature of the recycled gas after passing through the gas-liquid separator 8 is 5 degrees Celsius.

  Based on the temperature of the recycle gas after passing through the gas-liquid separator 8 detected by the temperature detector 30, the recycle gas flow rate is controlled by an instruction from the controller 38.

  Here, the flow rate of the recycle gas is adjusted in accordance with an instruction from the controller 38 using a correlation equation or a correlation table of the recycle gas temperature after passing through the gas-liquid separator 8 and the recycle gas flow rate. Is controlled by a device 44.

  In this embodiment, the preset O / C in the reformer 24 is 2.40.

  When the temperature of the recycle gas after passing through the gas-liquid separator 8 changes to 5 degrees Celsius, the recycle gas flow rate is changed to 0.36 SLM.

  Here, by the cooling in the gas-liquid separator 28, the water vapor 0.25 SLM in the hydrogen-containing gas is condensed and separated and discharged to the condensed water channel 32.

Here, the recycle gas composition is composed of CH ₄ : H ₂ : H ₂ O: CO: CO _{2 in} a ratio (molar ratio) of 24.9: 57.7: 0.9: 2.3: 14.2. Is done.

  The 2.03 SLM city gas supplied from the raw material supply path 34 merges with the recycle gas 0.36 SLM supplied from the recycle gas path and is supplied to the hydrodesulfurizer 22.

  Here, since the O / C of the recycle gas that merges from the recycle gas channel 26 to the raw material supply channel 34 is 0.76, the O / C of the merged gas in the reformer 24 is 2.40.

  As described above, the recycle gas supply amount is controlled based on the temperature of the recycle gas after passing through the gas-liquid separator 8 detected by the temperature detector 30, thereby passing through the gas-liquid separator 8. Even when the temperature of the recycled gas after the change is changed to 5 degrees Celsius, the O / C in the reformer 24 can be kept constant at 2.40. Therefore, even when the outside air temperature or the cooling water temperature is lowered, the possibility that carbon is precipitated in the reformer 24 can be reduced.

  In the present embodiment, the recycle gas flow rate is controlled using a correlation equation or a correlation table of the recycle gas temperature and the recycle gas flow rate after passing through the gas-liquid separator 8 prepared in advance. For example, a control method may be used in which a plurality of correlation equations or correlation tables are created, and the correlation equation or correlation table used for control is changed monthly.

(Third embodiment)
FIG. 5 is a block diagram illustrating an example of a schematic configuration of the hydrogen generator according to the third embodiment. Hereinafter, the hydrogen generator 130 of the third embodiment will be described with reference to FIG.

  In the example shown in FIG. 5, the hydrogen generator 130 includes an air supplier 46.

  The air supply unit 46 supplies air to the reformer 24. In the third embodiment, the reformer 24 may be a reformer that advances oxidative steam reforming (OSR). The air supply unit 46 may be composed of, for example, a pump and a needle valve. The air supply unit 46 is configured to be able to adjust the amount of air supplied to the reformer 24.

  When the temperature of the hydrogen-containing gas after passing through the gas-liquid separator 8 decreases, the controller 38 has a ratio of the oxygen-containing gas supply amount to the reformer 4 to the hydrogen-containing gas supply amount to the reformer 4. The air supply 46 is controlled to increase. That is, in the third example, the air supply unit 46 corresponds to the gas supply amount ratio adjuster 10 of the first embodiment. The oxygen-containing gas in the third embodiment includes air.

  When the temperature of the hydrogen-containing gas after passing through the gas-liquid separator 8 decreases, the controller 38 increases the air supply amount to the reformer 24 relative to the raw material supply amount to the reformer 24. The feeder 46 is controlled. At this time, the raw material supply amount to the reformer 24 may be constant.

  For example, when the required amount of hydrogen increases in the hydrogen utilization device that supplies the hydrogen-containing gas from the hydrogen generator 110 and the amount of raw material supplied to the reformer 24 increases, the raw material is supplied to the reformer 24. The amount of air supplied to the reformer 24 may be increased beyond the extent that the amount increases.

  For example, when the hydrogen generation apparatus 110 supplies hydrogen-containing gas and the required amount of hydrogen decreases in the hydrogen utilization device, the raw material supply amount to the reformer 24 decreases. The amount by which the amount of air supplied to the reformer 24 is increased may be reduced by the amount that is reduced.

  That is, “the air supply amount to the reformer increases with respect to the raw material supply amount to the reformer” is to increase the air supply amount relative to the raw material supply amount to the reformer 24. Say. Therefore, when the raw material supply amount to the reformer decreases, if the air supply amount increases relative to the raw material supply amount to the reformer 24, it is not necessary to increase the air supply amount. However, it may be decreased.

  Except for the above points, the controller 38 can have the same configuration as the controller 12 of the first embodiment.

  In addition, except for the above points, the hydrogen generator 130 can have the same configuration as the hydrogen generator 110 of the first embodiment. 5 and FIG. 2 are denoted by the same reference numerals and names, and detailed description thereof is omitted.

  Even if the temperature of the recycle gas after passing through the gas-liquid separator 8 is lowered, the amount of air supplied to the reformer 24 is increased, that is, the air supplied from the air supplier 46 to the reformer 24. By increasing the value, it is possible to suppress a decrease in O / C inside the reformer 24.

  Also in the present embodiment, the same modifications as in the first embodiment are possible. The first embodiment and the third embodiment may be combined. The second embodiment and the third embodiment may be combined. The first embodiment, the second embodiment, and the third embodiment may be combined.

(Example of simulation in the third embodiment)
In the configuration of FIG. 5, the simulation result when the operation is performed based on the third embodiment, that is, the temperature and flow rate of each fluid obtained from the calculation of each part of the system and the entire substance and energy balance will be described. The temperature of the recycled gas after passing through the gas-liquid separator 8 is 5 degrees Celsius.

  Based on the temperature of the recycle gas after passing through the gas-liquid separator 8 detected by the temperature detector 30, an air flow rate to the reformer 24 (hereinafter referred to as the reformed air flow rate) is instructed by the controller 38. ) To control.

  Here, the reformed air flow rate is prepared in accordance with an instruction from the controller 38 using a correlation equation or a correlation table of the temperature of the recycle gas after passing through the gas-liquid separator 8 and the reformed air flow rate. Controlled by the air supply 46.

  In this embodiment, the O / C in the reformer 24 is controlled to be 2.50.

  When the temperature of the recycle gas after passing through the gas-liquid separator 8 changes to 5 degrees Celsius, the recycle gas flow rate is changed to 0.73 SLM.

  Here, by the cooling in the gas-liquid separator 28, the water vapor 0.43 SLM in the hydrogen-containing gas is condensed and separated and discharged to the condensed water channel 32.

Here, the recycle gas composition is such that CH ₄ : H ₂ : H ₂ O: CO: CO ₂ : N ₂ is 20.0: 50.4: 0.9: 2.3: 13.9: 12.6. Consists of a ratio.

  The 2.03 SLM city gas supplied from the raw material supply path 34 joins the recycle gas 0.73 SLM supplied from the recycle gas path, and is supplied to the hydrodesulfurizer 22.

  Here, the O / C of the recycle gas that merges from the recycle gas flow path 26 to the raw material supply path 34 is 0.85, and the reformed air flow rate is 1.04 SLM. The O / C of the gas is 2.50.

  As described above, the reformed air flow rate is controlled based on the temperature of the recycle gas after passing through the gas-liquid separator 8 detected by the temperature detector 30, thereby passing through the gas-liquid separator 8. Even when the temperature of the later recycled gas changes to 5 degrees Celsius, the O / C in the reformer 24 can be kept constant at 2.50. Therefore, even when the outside air temperature or the cooling water temperature is lowered, the possibility that carbon is precipitated in the reformer 24 can be reduced.

(Second Embodiment)
The operation method of the hydrogen generator of the second embodiment is the operation method of the hydrogen generator of the first embodiment, and further, when the temperature of the hydrogen-containing gas that has undergone the gas-liquid separation step rises, to the reformer At least one of a step of reducing the ratio of the oxygen-containing gas supply amount to the reformer with respect to the raw material supply amount, and a step of increasing the ratio of the hydrogen-containing gas flowing into the recycle channel among the hydrogen-containing gas Is provided.

  The hydrogen generator of the second embodiment is the hydrogen generator of the first embodiment, and when the controller increases the temperature of the hydrogen-containing gas after passing through the gas-liquid separator, the raw material to the reformer The ratio of the oxygen-containing gas supply amount to the reformer with respect to the supply amount is decreased, and / or the ratio of the hydrogen-containing gas flowing into the recycle channel among the hydrogen-containing gas is increased. The gas supply amount ratio adjuster is configured to be controlled.

  In such a configuration, even if the temperature of the hydrogen-containing gas after passing through the gas-liquid separator rises, the ratio of the oxygen-containing gas supply amount to the reformer with respect to the hydrogen-containing gas supply amount to the reformer is not reduced. Compared to the case, the power generation efficiency can be maintained higher.

  The hardware configuration of the hydrogen generator of this embodiment can be the same as that of the hydrogen generator 100 of the first embodiment. Therefore, the same reference numerals and names are assigned to components common to those in FIG.

  In the present embodiment, when the temperature of the hydrogen-containing gas after passing through the gas-liquid separator 8 increases, the controller 12 supplies the oxygen-containing gas to the reformer 4 with respect to the raw material supply amount to the reformer 4. The gas supply amount ratio adjuster 10 is controlled so as to execute at least one of a decrease in the ratio and a ratio of the hydrogen-containing gas flowing into the recycle channel 6 among the hydrogen-containing gas. .

  Specifically, for example, as in the first embodiment, when the gas supply amount ratio adjuster 10 is a water vapor supply device and the oxygen-containing gas is water vapor, the controller 12 is a gas-liquid separator. When the temperature of the hydrogen-containing gas after passing through 8 rises, the steam supply unit may be controlled so that the steam supply amount to the reformer 4 with respect to the raw material supply amount to the reformer 4 decreases.

  Note that “the steam supply amount to the reformer decreases with respect to the raw material supply amount to the reformer” means that the steam supply amount decreases relative to the raw material supply amount to the reformer. . Therefore, when the production amount of the hydrogen-containing gas increases, if the steam supply amount is decreased relative to the raw material supply amount to the reformer, the steam supply amount may be decreased, or the steam supply amount. May be increased.

  Or, for example, when the gas supply amount ratio adjuster 10 is a flow rate adjuster as in the second embodiment, the controller 12 increases the temperature of the hydrogen-containing gas after passing through the gas-liquid separator 8. Then, you may control a flow regulator so that the ratio of the hydrogen containing gas which flows into the recycle flow path 6 among hydrogen containing gas may increase.

  “The ratio of the hydrogen-containing gas flowing into the recycle channel among the hydrogen-containing gases increases” means that the hydrogen-containing gas flowing into the recycle gas channel with respect to the amount of hydrogen-containing gas generated by the reformer It means to increase the ratio of the amount of. Therefore, when the amount of hydrogen-containing gas produced by the reformer decreases, the hydrogen-containing gas supply amount flowing through the recycle gas flow path is relatively set with respect to the amount of hydrogen-containing gas produced by the reformer. If it increases, the supply amount of the hydrogen-containing gas flowing through the recycle gas passage may not be increased or may be decreased.

  Alternatively, for example, as in the third embodiment, when the gas supply amount ratio adjuster 10 is an air supply and the oxygen-containing gas is air, the controller 12 passes through the gas-liquid separator 8. When the temperature of the subsequent hydrogen-containing gas rises, the steam supply device may be controlled so that the air supply amount to the reformer 4 with respect to the raw material supply amount to the reformer 4 decreases.

  Note that “the air supply amount to the reformer decreases with respect to the raw material supply amount to the reformer” means that the air supply amount decreases relative to the raw material supply amount to the reformer. . Therefore, when the amount of hydrogen-containing gas produced increases, the air supply amount may or may not be decreased if the air supply amount is decreased relative to the raw material supply amount to the reformer. Also good.

  Or you may combine the said structure arbitrarily.

  Except for the above points, the hydrogen generator of this embodiment can have the same configuration as the hydrogen generator 100 of the first embodiment.

  According to the hydrogen generator of this embodiment, O / C in the reformer 4 can be appropriately controlled according to the temperature of the recycled gas after cooling, and the power generation efficiency can be kept higher.

(Third embodiment)
A fuel cell system according to a third embodiment includes a hydrogen generation apparatus according to any one of the first embodiment, the first example, the second example, the third example, the second embodiment, and modifications thereof, and hydrogen generation. And a fuel cell that generates electric power using the hydrogen-containing gas supplied from the apparatus.

  With such a configuration, it is possible to reduce adverse effects caused by temperature fluctuations of the hydrogen-containing gas recycled to the hydrodesulfurizer.

  FIG. 6 is a block diagram showing an example of a schematic configuration of a fuel cell system according to the third embodiment. Hereinafter, the fuel cell system 200 of the third embodiment will be described with reference to FIG.

  In the example shown in FIG. 6, the fuel cell system 200 includes a fuel cell 20. The fuel cell 20 generates power using the hydrogen-containing gas supplied from the hydrogen generator 100. The fuel cell 20 includes an anode and a cathode, and may generate power using a hydrogen-containing gas supplied from the reformer 4 to the anode and air supplied to the cathode.

  The fuel cell 20 may be of any type, and examples thereof include polymer electrolyte fuel cells, solid oxide fuel cells, phosphoric acid fuel cells, and molten carbonate fuel cells. When the fuel cell 20 is a solid oxide fuel cell, the reformer and the fuel cell are configured to be built in one container.

  Also in this embodiment, the same modifications as those of the first embodiment, the first example, the second example, the third example, and the second embodiment are possible.

  From the foregoing description, many modifications and other embodiments of the present invention are obvious to one skilled in the art. Accordingly, the foregoing description should be construed as illustrative only and is provided for the purpose of teaching those skilled in the art the best mode of carrying out the invention. The details of the structure and / or function may be substantially changed without departing from the spirit of the invention.

  One embodiment of the present invention is useful as a hydrogen generator, an operating method thereof, and a fuel cell system that can reduce adverse effects caused by temperature fluctuations of a hydrogen-containing gas recycled to a hydrodesulfurizer.

2 Hydrodesulfurizer 4 Reformer 6 Recycle channel 8 Gas-liquid separator 10 Gas supply ratio adjuster 12 Controller 20 Fuel cell 22 Hydrodesulfurizer 24 Reformer 26 Recycle gas channel 28 Gas-liquid separator DESCRIPTION OF SYMBOLS 30 Temperature detector 32 Condensed water flow path 34 Raw material supply path 36 Water vapor supply apparatus 38 Controller 40 Water vapor supply path 42 Hydrogen-containing gas flow path 44 Flow regulator 46 Air supply apparatus 100 Hydrogen generation apparatus 110 Hydrogen generation apparatus 120 Hydrogen generation apparatus 130 Hydrogen generator 200 Fuel cell system

Claims (9)

Removing a sulfur compound in the raw material with a hydrodesulfurizer;
A step of generating a hydrogen-containing gas by using a raw material supplied from steam and the hydrodesulfurizer by a reformer;
When a flow path for recycling a part of the hydrogen-containing gas and supplying it to the hydrodesulfurizer is a recycle flow path, the hydrogen-containing gas before flowing into the recycle flow path and the recycle flow path A step in which at least one of the subsequent hydrogen-containing gas is cooled and the condensed water generated from the hydrogen-containing gas is gas-liquid separated; and
A step of increasing a ratio of an oxygen-containing gas supply amount to the reformer with respect to a raw material supply amount to the reformer when the temperature of the hydrogen-containing gas that has undergone the gas-liquid separation step decreases, and the hydrogen-containing gas And a step of reducing the ratio of the hydrogen-containing gas flowing into the recycle flow path.   The step of increasing the ratio of the oxygen-containing gas supply amount to the raw material supply amount to the reformer is a step of increasing the ratio of the steam supply amount to the reformer to the raw material supply amount to the reformer. The operation method of the hydrogen generator according to claim 1.   The step of increasing the ratio of the oxygen-containing gas supply amount to the raw material supply amount to the reformer increases the ratio of the reforming air supply amount to the reformer with respect to the raw material supply amount to the reformer. The operation method of the hydrogen generator according to claim 1, which is a step.   Further, when the temperature of the hydrogen-containing gas that has undergone the gas-liquid separation step increases, the ratio of the oxygen-containing gas supply amount to the reformer with respect to the raw material supply amount to the reformer is reduced, and the hydrogen The operation method of the hydrogen generator according to any one of claims 1 to 3, further comprising at least one of a step of increasing a ratio of a hydrogen-containing gas flowing into the recycle channel among the contained gases. A hydrodesulfurizer that removes sulfur compounds in the raw material;
A reformer that generates hydrogen-containing gas using steam and a raw material supplied from the hydrodesulfurizer;
A recycling flow path for recycling a part of the hydrogen-containing gas discharged from the reformer and supplying it to the hydrodesulfurizer;
A gas-liquid separator that cools at least one of the hydrogen-containing gas before flowing into the recycle channel and the hydrogen-containing gas after flowing into the recycle channel, and condenses and separates moisture in the hydrogen-containing gas;
A gas that adjusts at least one of the ratio of the oxygen-containing gas supply amount to the reformer relative to the raw material supply amount to the reformer and the ratio of the hydrogen-containing gas flowing into the recycle channel among the hydrogen-containing gas A supply ratio adjuster;
When the temperature of the hydrogen-containing gas after passing through the gas-liquid separator decreases, the ratio of the oxygen-containing gas supply amount to the reformer with respect to the raw material supply amount to the reformer is increased, and the hydrogen-containing gas And a controller for controlling the gas supply amount ratio adjuster so as to execute at least one of reducing the ratio of the hydrogen-containing gas flowing into the recycle flow path. The gas supply amount ratio adjuster includes a steam supply unit that supplies steam to the reformer,
The controller increases the ratio of the oxygen-containing gas supply amount to the reformer with respect to the hydrogen-containing gas supply amount to the reformer by increasing the steam supply amount to the reformer. It is configured,
The hydrogen generator according to claim 5. The gas supply amount ratio adjuster includes an air supply for supplying air to the reformer,
The controller increases a ratio of an oxygen-containing gas supply amount to the reformer with respect to a hydrogen-containing gas supply amount to the reformer by increasing an air supply amount to the reformer. It is configured,
The hydrogen generator according to claim 5. When the temperature of the hydrogen-containing gas after passing through the gas-liquid separator increases, the controller decreases the ratio of the oxygen-containing gas supply amount to the reformer with respect to the raw material supply amount to the reformer. And the gas supply amount ratio adjuster is configured to control at least one of increasing a ratio of the hydrogen-containing gas flowing into the recycling flow path among the hydrogen-containing gas. ing,
The hydrogen generator according to any one of claims 5 to 7. A hydrogen generator according to any one of claims 5 to 8,
And a fuel cell that generates electricity using the hydrogen-containing gas supplied from the hydrogen generator.

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